Detergent composition containing phosphonio sulfonates



United States Patent 3 390,095 DETERGENT COMPOSITION CONTAININGPHOSPHONIO SULFONATES Francis L. Diehl, Wyoming, Ohio, assignor to TheProcter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio NoDrawing. Filed Mar. 14, 1966, Ser. No. 533,858 Claims. (Cl. 252--138)ABSTRACT OF THE DISCLOSURE Detergent compositions with superior coolwater laundering effectiveness comprising a phosphonio sulfonate havinga long chain alkyl and an alkaline builder salt.

This invention relates to detergent compositions containing phosphoniosulfonates which are especially effective in cool water. The term coolwater as used in describing this invention is intended to mean aqueouswashing solutions having a temperature within a range of from about 40F. to about 95 F. This temperature characterization more generally isintended to mean temperatures substantially below those which arecommonly associated with the usual household parlance of hot water.

Some garments or fabrics cannot be washed in hot water, i.e., say inexcess of about 110 F., without running the risk of damaging thematerial by shrink-age or altering the handle or feel of the fabric orby adversely affecting dyes or by increasing wrinkling in wash and wearor minimum care garments. For such laundering situations fabric andmaterial manufacturers recommend the use of cool water. Conventionaldetergents, however, are known to be less effective as cleaning agents,i.e., removing soil, in cool aqueous solutions. There is no questionthat the presently available deter-gent compositions can be used undersuch circumstances but with varying degrees of successful cleaningresults. To compensate for the poorer cleaning performance, consumersare generally inclined to use excessive amounts of the detergentcompositions. Such economic waste is unfortunate but has been necessaryprior to the present invention due to the lack of detergent compositionswhich are specially formulated to be effective cleaning agents in coolwater.

It is an object of this invention to provide a detergent compositionwhich is especially effective in cleaning soiled fabrics in cool aqueouswashing solutions and a method for using such a composition inlaundering with cool water.

Other objects will be readily apparent to those skilled in the art froma review of the following detailed description of the present invention.

This object of the present invention is achieved with novel builtdetergent compositions consisting essentially of (1) a phosphoniosu'lfon-ate detergent compound having the general formula:

69 e R1-P-CI'IgR CH2-SO3 R is an alkyl group containing from 12 to 116carbon atoms; R and R are each alkyl or hydroxy alkyl groups containingfrom 1 to 4 carbon atoms; R, is C H X wherein n is 0, l or 2 and X is Hor OH, and (2) a water soluble inorganic alkaline builder salt, anorganic alkaline sequestrant builder salt or mixtures thereof, the ratioof weight of the detergent to the builder salt being in the range offrom about 4:1 to 1:20.

It has now been surprisingly discovered that certain phosphoniosulfonate compounds having; the formula set forth above possessunusually effective cleaning power in aqueous solutions having the cooltemperatures defined above. These unexpected cleaning properties of thecompounds of this invention are demonstrated by the experimental datapresented below. Of the phosphonio sulfonate detergent compoundsdescribed herein, best cool water cleaning results are obtained when R;is dodecyl, R and R are each methyl and R is CH The sulfonate compoundsto which the present invention pertains can be prepared according to anyconvenient process. The R alkyl can be derived. from synthetic sourcessuch as alkyl bromides, synthetic alcohol, e.g. dodecanol, or fromnatural sources such as coconut oil or tallow from which fatty alcoholsare made. Such processes are noted hereinafter but other methods can beused.

The phosphonio sulfonates can be made by the processes described in US.Patent 2,828,332 issued Mar. 25, 1958, to Van R. Gaertner.

While the class of sulfonate compounds just described can be employedalone as cool water detergent compounds on easily cleanable materials,more outstanding performances are obtained when they are mixed withother ingredients which enhance or build the cleaning power of detergentcompounds, i.e., so-called builders or detergency-enhancing compounds.Such built or heavy-duty deter-gency is essential with hard-to-cleanfabrics such as cotton. According to the present invention, therefore,the sulfonate detergent compounds are preferably used in conjunctionwith such other ingredients which substantially improve cleaning power.While the term builder is used herein in its singular form, the term isintended to cover mixtures of such compounds also.

The present invention pertains to detergent compositions consistingessentially of a water soluble inorganic alkaline builder salt or awater soluble organic alkaline sequ-estrant builder salt, or mixturesthereof, and a member of the class of su-lfonate detergent compoundshaving the general formula described above, which composition consistsessentially of the detergent compounds and a builder material in a ratioby weight of detergent to builder of about 4:1 to about 1:20. Thepreferred ratio of the deter-gent to builder is lz 1 to about 1:10. Theratios and percentages referred to herein are all by weight unlessotherwise noted.

The built detergent compositions of this invention can be prepared asgranular, tablet, or liquid compositions and perform effectively. Withinthe above detergent to builder ratio range, granular and tabletcompositions offering outstanding cool water washing performance cancontain from 4% to 50% by weight of the sulfonate detergent compound,the balance comprising essentially a selected builder material ormixtures of builders and any optional ingredients employed. Preferredgranular and tablet compositions contain from about 15% to about 35% byweight of the sulfonate detergent with the balance comprising theessential builder materials and other ingredients. On the other hand,built liquid detergents prepared according to the present invention havea slightly modified composition to compensate for the requirement of aliquid vehicle. Such liquid compositions can contain from about 2% to25% by weight of the sulfonate detergent, preferably from about 8% toabout 18%, with the remainder comprised essentially of builderingredients, and, of course, a liquid vehicle as described below. Theratio set forth above between the detergent and builder applies equallyto all physicl forms of the composition.

Water soluble inorganic alkaline builder salts which can be used in thisinvention alone or in admixture are alkali metal carbonates, borates,phosphates, polyphosphates, bicarbonates and silicates. Ammonium orsubstituted ammonium, e.g., triethanol ammonium, salts of thesematerials can also be used. Specific examples of suit able salts aresodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodiumand potassium pyrophosphate, sodium and ammonium bicarbonate, potassiumtripolyphosphate, sodium hexaphosphate, sodium sesquicarbonate, sodiumorthophosphate and potassium bicarbonate. The preferred inorganicalkaline builders according to this invention are alkali metaltripolyphosphates for built granular and tablet compositions and alkalimetal pyrophosphates for built liquid compositions. Potassium is thepreferred alkali metal used in liquid compositions and sodium finds bestapplication for granular or tablet compositions.

Examples of suitable organic alkaline sequestrant builder salts used inthis invention alone or in admixture are alkali metal, ammonium orsubstituted ammonium, aminocarboxylates, e.g., sodium and potassiumethylenediaminetetraacetate, sodium and potassiumN-(Z-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassiumnitrilotriacetates and sodium, potassium and triethanolammonium N (2hydroxyethyl) nitrilodiacetates. Mixed salts of these polycarboxylatesare also suitable. The alkali metal salts of phytic acid, e.g., sodiumphytate are also suitable as organic alkaline sequestrant builder salts(see U.S. Patent 2,739,942).

Polyphosphonates are also valuable builders in terms of the presentinvention including specifically sodium and potassium salts ofethane-l-hydroxy-l, l-diphosphonate, sodium and potassium salts ofmethylene diphosphonate, sodium and potassium salts of ethylenediphosphonate, and sodium and potassium salts ofethane-1,1,2-triphosphonate. Other examples include the alkali metalsalts of ethane-2-carboxy-1,1-diphosphonic acid,hydroxymethanediphosphonic acid, carbonyldiphosphonic acid,ethane-l-hydroxy-1,1,2-triphosphonic acid, ethaneZ-hydroxy-l,1,2-triphosphonic acid, propane-1,1,3,3-tetraphosphonicacid, propane-1,1,2,3-tetraphosphonic acid, andpropane-1,2,2,3-tetraphosphonic acid.

Besides the builders being used in the form of mixtures it is alsopossible according to the present invention to use the phosphoniosulfonate compounds of this invention in combination with other cleaningagents such as anionic, nonionic, ampholytic and zwitterionic organicdetergent surfactant compounds. When it is desired to use such sulfonatecompounds in combination with other detergent compounds, they arepreferably utilized with anionic detergents because of the sudsingcharacteristics of the latter. The ratio of the sulfonate to such otherdetergent compound is about 10:1 to 1:5. If it is desired to use such aphosphonio sulfonate in admixture with another detergent compound as theactive portion of a cleaning composition, the ratio of such amixture tothe builder salt should be within the previously prescribed range of 4:1to 1:20. A composition prepared along these lines can contain from 4% to50% of such a mixture and 5% to 85% of a builder salt selected fromwater soluble inorganic alkaline builder salts, water soluble organicsequestrant builder salts, and mixtures thereof, within the prescribedratio range.

Examples of anionic soap detergents which can be used in admixture withthe sulfonate detergent, if desired, are the sodium, potassium, ammoniumand alkylolammonium salts of higher detergent range fatty acids (C CParticularly useful are the sodium and potassium salts of the mixturesof fatty acids derived from coconut oil and tallow, i.e., sodium orpotassium tallow and coconut soap. Examples of suitable anionic organicnonsoap detergents in the form of their water soluble salts are:alkylglycerylether sulfonates; alkyl sulfates; alkyl monoglyceridesulfates or sulfonates; alkylpolyethenoxy ether sulfates;acylsarcosinates; acyl esters of isethionates; N-acyl-N-methyl taurides,alkylbenzene sulfonates wherein the alkyl substituent is straight chainor branched chain;

sulfonated ot-olefins; alkylphenol polyethenoxy sulfonates. In thesecompounds the alkyl and acyl groups, respectively, contain 10 to 20carbon atoms. They are used in the form of water soluble salts, thesodium, potassium, ammonium, and alkylolammonium salts, for example.Specific examples are: sodium lauryl sulfate, sodium tallow alkylsulfate; sodium salt of sulfonated zx tridecene; potassiumN-methyl-N-lauroyl tauride; triethanolammonium tetrapropylbenzenesulfonate; soduim (linear) dodecyl benzene sulfonate.

Examples of nonionic organic detergents which can be used in thecompositions of this invention, if desired, are: polyethylene oxidecondensates of alkylphenols wherein the alkyl group contains from 8 to15 carbon atoms (e.g., t-octylphenol) and the ethylene oxide is presentin a molar ratio of ethylene oxide to alkylphenol in the range of 8:1 to20:1; condensation products of ethylene oxide with the product resultingfrom the reaction of propylene oxide and ethylene diamine wherein themolecular weight of the condensation products ranges from 5000 to11,000; the condensation products of from about 5 to 30 moles ofethylene oxide with one mole of a straight or branched chain aliphaticalcohol containing from 8 to 18 carbon atoms, e.g., condensation productof 6 moles of ethylene oxide with one mole of lauryl alcohol; higheralkyl di-lower alkyl amine or phosphine oxides, e.g.,dodecyldimethylamine oxide or dodecyldimethly phosphine oxide; alkylmethyl sulfoxides such as dodecyl methyl sulfoxide.

Ampholytic synthetic detergents can be broadly described as derivativesof aliphatic secondary and tertiary amines in which the aliphaticradical can be straight chain or branched and wherein one of thealiphatic substituents contains from about 8 to about 18 carbon atomsand one contains an anionic water solubilizing group, e.g., carboxy,sulfonate, sulfate, phosphate, or phosphonate. Examples of compoundsfalling within this definition are sodium 3-dodecylaminopropionate,3-(N-methyl-N-hexadecylamine)-2-hydroxy propane-l-sulfonate and itsdodecyl homolog, sodium 3-dodecylaminopropane sulfonate,dodecyl-beta-alanine, N-alkyltaurines such as the one prepared byreacting dodecylamine with sodium isethionate according to the teachingof United States Patent No. 2,658,072, N-higher alkyl aspartic acidssuch as those produced according to the teaching of United States PatentNo. 2,438,091, and the products sold under the trade name Miranol anddescribed in United States Patent No. 2,528,378.

Zwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium, phosphonium, and sulfoniumcompounds, in which the aliphatic radical may be straight chain orbranched, and wherein one of the aliphatic substituents contains fromabout 18 carbon atoms and one contains an anionic water solubilizationgroup, e.g., carboxy, sulfo, or sulfato. Examples of compounds fallingwithin this definition are: 3(N,N-dimethyl-N-hexadecylamrnonio)-2-hydroxypropane-l-sulfonate and thecorresponding dodecyl and tetradecyl homologs and3-(N,N-dimethyl-N-dodecylammonio)-propanel-sulfonate and thecorresponding hexadecyl and tetradecyl homologs.

The discovery that the compositions containing mem bers of the class ofcompounds described in this invention show exceptional cool waterdetergency was unpredictable in view of the fact that there is, as yet,virtually no generally accepted theory or background information on themechanics of cool water detergency. Moreover, cleaning agents such assodium tallow alcohol sulfate or sodium dodecylbenzenesulfonate, forexample, which are good hot water (-140 F.) detergent compounds exhibita minimum of cleaning activity in cool water. One would be led to assumethat the sulfonate compounds of the present invention should be,comparatively speaking, as poor as any other conventional detergentcompounds I. when used in cool water; certainly there is no reason toexpect that they would behave otherwise. As has been discovered,however, the compositions containing the sulfonate compounds of thisinvention are substantially more effective in cool water than some ofthe commonly used commercially available detergent compositions are inhot water. It can, therefore, be seen that the structure of a givendetergent compound which is effective in hot water has little or nodiscernible relation to the effectiveness of such compounds in coolwater.

It has also been found that maximum cleaning occurs with thecompositions of this invention when the pH of the washing solution, atcool water temperatures as herein defined is within the range of fromabout 8 to about 12 with the preferred pH range being 9.5 to 11.5. Usingnormal amounts of water for washing, the desired pH of the solution canbe obtained by incorporating into the compositions of this invention anormal amount of a strongly alkaline material such as Sodium silicate,i.e., up to about by weight. The silicate acts as a buffer and also as acorrosion inhibitor.

A laundering method incorporating the discovery of the present inventioncan be practiced in a number of different ways. Preferably the washingstep is followed by rinsing and drying the fabrics. The washing solutioncan be prepared by adding the granular, tablet or liquid detergentcomposition prepared according to this invention to any container whichcontains cool water at a temperature ranging from about 40 F. to about95 F., usually about 80 F. The detergent composition concentration insolution can range from about .05% to .50% by total weight in the usualwashing operation and should be added in sufficient amount to provide aconcentration of at least 0.005% of the phosphonio sulfonate detergentcompound. The fabrics can be added to the container or washer before orafter the washing solution is added. As is usual in a washin step, thefabrics are then agitated in the detergent solution. While the period oftime may vary, an automatic agitator type washer, generally employs awashing cycle which ranges from 8 to minutes. In special situations,such as hand washing in basins, pools or streams, higher compositionconcentrations can be employed including solutions or pastes of up to5%, 25% or even 50% and higher.

After the washing step, the washing liquor is drained off or the fabricsare separated from the liquor and thereafter the fabrics are rinsed inclean water. The fabrics can be rinsed as many times as desired in orderto insure that washing liquor is removed. Using an automatic washer, ithas been found that about four spray rinses and one deep rinse areusually sufficient for this purpose. Between and after rinsing steps,the bulk of the rinse water is usually drawn from or spun out of thefabrics. After rinsing, the fabrics are dried. Although rinsing anddrying are usual and desirable steps, the important advantage of theinvention is achieved in the washing step.

The surprisingly effective cool water performance characteristics of thesulfonate compounds described herein are demonstrated by conducting thefollowing tests.

Naturally soiled fabric swatches (desized cotton print cloth) werewashed for ten minutes in an aqueous solution of a detergent compositionhaving a pH of 10 and containing 7 grains equivalent CaCO hardness pergallon. Detergent compositions were prepared containing only basicessentials, i.e., a detergent compound and a builder compound. Thedetergent compounds were respectively (1) a representative phosphoniosulfonate and (2) sodium tetrapropylenebenzene sulfonate (ABS); thebuilder compound in each composition was sodium tripolyphosphate. Thephosphonio sulfonate compound was 3-(P,P-dimethyl, P-dodecylphosphonio)propane l sulfonate (DMDPPS) By using the samebuilder compound in each composition, any variations in cleaningperformance could be directly attributed to the specific detergent beingevaluated. The

Compound Temperature, F. Soil Removal, Percent The phosphonio sulfonatedetergent compounds gave results, in this test, in water at 80 P. whichwere superior to the results obtained with a formula wherein sodiumtetrapropylenebenzene sulfonate (ABS) was used as a cleaning agent in awashing solution having a temperature of 140 F. Sodiumtetrapropylenebenzene sulfonate is widely regarded as a standard forcomparison. Compositions which perform better than ABS at 140 F.generally can find application and commercial acceptance as detergentformulations. In situations such as the present invention where superiorcleaning is obtained with different compounds at low temperatures, i.e.,80 F., the results are even more remarkable.

The same superiority of the phosphonio sulfonate compounds at 80 F. overABS at 140 F. was demonstrated in a similar washing test employingsoiled me'ns white dress shirts where the collars and cuffs were used asthe basis for comparing cleaning ability of compositions employing thesetwo detergent compounds. The superior cleaning ability of the phosphoniosulfonate compounds was particularly manifested in the whiteness of thecollars and cuffs.

Substantially the same performance advantages are observed by thehousewife when doing the home laundry in water ranging from 40 to 95 F.Woolens and synthetic fibers washed in the same manner are cleaned asefficiently when washed according to the process of this invention andusing the compositions of this invention as they would be if they werewashed in conventional detergent compositions at hot water temperatures,yet a minimum of shrinkage and wrinkling takes place and the feel of thewool is preserved to a greater extent.

While the compositions of this invention are outstandingly effective inwater at a temperature ranging from 40 F. to 95 F. the preferredtemperature range is about 60 F. to F. Below about 60 F. it has beenfound that the granular detergent compositions of this invention aresomewhat slower to dissolve, consequently it is preferred to use liquidcompositions at such lower temperatures.

The following compositions further illustrate the manner in which theinvention can be practiced; they provide improved cool water detergencycharacteristics similar to that demonstrated in the soil removalcomparison set forth above. The pHs of each of the compositions inaqueous solutions ranged from 9.5 to 11.5 at concentrations of about0.25%. Included are :both liquid and granular formulations. Mixtures ofthe phosphonio sulfonates and other detergents can be used. The examplesare not to be construed as limiting the scope of the invention claimedhereinafter. These compositions are useful in automatic washers andconventional type washers employing cool water, 40 F. to F., as well ashand washing operations.

7 EXAMPLE I SolidGranules Percent 3-(P,P-dibutyl, P-dodecylphsphonio)propane-1- sulfonate 7.5 Sodium tripolyphosphate 50 Sodiumsilicate (Na O:SiO =1:2.5) 10.0 Moisture 5.0

EXAMPLE II Compressed granulesTablet Percent 3(P,P-diethyl, P-tetradecylphosphonio)propane-1- sulfonate 31 Tetrasodium pyrophosphate 52Trisodium phosphate a- Moisture 7 EXAMPLE III SolidGranules Percent2-(P,P-bis(2hydroxyethyl), P-hexadecyl phosphonio)ethane-l-sulfonate 32Trisodium ethane-l-hydroxy 1,1,2 triphosphonate 64 Moisture 4 EXAMPLE IVSolid-Granules Percent 3-(N,N-dimethyl-N-hexadecyl ammonio)propane-1-sulfonate 3-(P,P-dipropyl-P-dodecylphosphonio)-2-hydroxypropane-I-sulfonate Sodium tripolyphosphate Sodiumcarbonate 10 Sodium silicate (N21 O:SiO =1:2.5) 5 Moisture 5 EXAMPLE VSolid-Granules Percent 3- (P,P-dimethyl, P-dodecylphosphonio)propanc-lsulfonate 20' Sodium tallow alcohol sulfate 10Trisodium ethane-l-hydroxy-l,l-diphosphonate 20 Sodium tripolyphosphate10 Sodium nitrilotriacetate 10 Sodium sulfiate 8 Sodium silicate (Na-O:SiO =1:2.5) 11 Moisture 11 EXAMPLE VI Liquid Percent4-(P,P-dimethyLP-phosphonio)-2-hydroxy butanel-sulfonte 5.0 Sodium saltof S0 sulfonated 1:1 weight mixture of dodecene and ix-tetradecene 10.0Tetrapotassium pyrop'hosphate 19.0 Sodium silicate (N21 O:SiO =1:1.6 3.8Potassium toluene sulfonate 8.5 Carboxymethyl hydroxyethyl cellulose .3Water Bal.

EXAMPLE VII Liquid Percent 3-(P,P-bis(2-hydroxypropyl) Pdodecylphosphonio)propane-1-sulfonate 6.0 Sodium (linear) dodecylbenzene sulfonate 6.0

Tetra otassium propane-1,1,3,3-tetraphosphonate 20.0

EXAMPLE VIII Solid-Granules Percent 4-(P,P dipropyl,P-dodecylphosphonio)butane-lsulfonate 5 Condensation product of 10 molesof ethylene oxide and one mole of tallow fatty alcohol 5 Sodium (linear)tridecyl benzene sulfonate 10 Dodecyldimethyl phosphine oxide 5 Coconutoil soap 5 Sodium tripolyphosph ate 50 Tetrasodium ethylene diaminetetraacetate 20 It will 'be appreciated that the phosphonio sulfonatecompounds used in the present invention can be incorporated into manyother liquid or granular detergent compositions with suitableadjustments being made in the other components.

Materials which are considered normal and desirable additives in liquidor granule detergent compositions can be added to the compositions ofthis invention without adversely affecting or modifying basic cleaningcharacteristics. For example, a tarnish inhibitor such as benzotriazoleor ethylene thiourea may be added in amounts up to about 1%.Fluorescers, perfume, bleaching agents, color, antiredeposition agents,antibacterial agents, thickening agents, opacifiers, and blending orviscosity control agents, while not essential in the compositions ofthis invention, may also be added.

While the present invention finds exceptional appl cation in cool waterwashing situations, the compositions described herein can also be usedin conjunction with warm and hot water.

What is claimed herein is:

1. A detergent composition having superior cleaning ability in aqueoussolutions having a temperature within a range of from about 40 F. toabout F. consisting essentially of (1) a phosphonio sulfonate detergentcompound of the following general formula:

R is an alkyl group containing from 12 to 16 carbon atoms; R and R areeach alkyl or hydroxy alkyl groups containing from 1 to 4 carbon atoms;R is C H X wherein n is 0, 1 or 2 and X is H or OH and (2) a buildermaterial selected from the group consisting of water soluble inorganicalkaline builder salts, organic alkaline sequestrant builder salts, andmixtures thereof, the ratio by weight of said detergent compound to saidbuilder material being in the range of about 4:1 to about 1:20.

2. The detergent composition of claim 1 wherein the ratio of saiddetergent compound to said builder is from 1:1 to about 1:10, by weight.

3. The detergent composition of claim 2 in which the aqueous solutionhas a pH of from about 8 to about 12.

4. The detergent composition of claim 3 wherein the preferred pH rangeis between about 9.5 and 11.5.

5. The detergent composition of claim 3, wherein said builder materialis sodium tripolyphosphate.

6. The detergent composition of claim 3 wherein the detergent compoundis 3-(P,P dimethyl, P-dodecyl phosphonio)propane-l-sulfonate.

7. The detergent composition of claim 5 wherein the detergent compoundis 3-(P,P-dimethyl, P-dodecyl phosphonio) propane-l-sulfonate.

8. A laundering process comprising the steps of immersing soiled fabricsand garments into an aqueous solution having a temperature within therange of from about 40 F. to about 95 F.', and a pH of from about 8 toabout 12, said aqueous solution containing at least about .05% by weightof the detergent composition of claim 1.

9 10 9. The process of claim 8 wherein the detergent com- ReferencesCited POSltlOIl 18 that Of claim UNITED 10. A .bullt detergentcomposition consisting essentially of 4 to 50% of a mixture of thesulfon-ate cleter- 21828332 3/1958 Gaermfir 2605O5 gent compound ofclaim 1 and an organic anionic deter- 5 FO GN PATENTS gent, the ratio ofthe compound to said organic deter- I P gent being in the range of 10:1to 1:5 and from 5 to 937949 1/1956 Gdmany' 85% of a builder materialselected from the group con- LEON D ROSDOL Primal? Examiner sisting ofwater soluble inorganic alkaline builder salts, water soluble organicalkaline sequestrant builder salts, 10 WILLIS, AS51510! and mixturesthereof.

